The present invention relates to a resin composition comprising a synthetic resin and a powdered magnetic material, and particularly to a resin composition which comprises, as a powdered magnetic material, soft ferrite powder having a low rate of permeability change by temperature and can be suitably used in a field of filters such as duplexers and multiplexers, and a molded or formed product from such a resin composition.
Compounds (MOxc2x7Fe2O3) composed of ferric oxide and an oxide of a divalent metal are soft magnetic materials exhibiting a high permeability and generally called soft ferrite. Sinter molded or formed products from soft ferrite such as Nixe2x80x94Zn ferrite, Mgxe2x80x94Zn ferrite or Mnxe2x80x94Zn ferrite are widely used as, for example, magnetic cores for radios, televisions, communication equipment, OA apparatus, inductors for switching power sources and the like, transformers, filters, etc.; head cores for video or image apparatus and magnetic disk apparatus; and the like.
In recent years, composite materials (resin compositions) obtained by dispersing a powdered magnetic material in a polymer have attracted attention as new magnetic materials, since they can be formed into molded or formed products of desired shapes and sizes by melt processing processes such as injection molding, extrusion and compression molding. Resin compositions making use of soft ferrite powder as a powdered magnetic material have also been proposed. However, the soft ferrite powder tends to undergo changes in its magnetic properties, for example, reduction in effective permeability by the formation of its composite with a synthetic resin. Therefore, the application fields of the resin compositions comprising the synthetic resin and soft ferrite powder are limited under the circumstances to choke coils, rotary transformers, electromagnetic wave shielding materials, etc.
Investigations have heretofore been made to apply resin compositions comprising a synthetic resin and soft ferrite powder to an application field of noise filters. A filter has a function that an electric current within a certain frequency band is caused to pass through, and great attenuation is given to electric currents within other frequency bands than that frequency band. Such a resin composition may be used as a various kinds of noise filters that suppress noises in a wide frequency band. Since the resin composition has a too high rate of permeability change by temperature, however, it has involved a problem that in a field of filters such as duplexers and multiplexers that perform a separation of a specific frequency band, or the like, the frequency band to be separated varies due to changes in environmental temperature, resulting in a failure to use it.
More specifically, in the conventional resin compositions making use of soft ferrite powder, the rate of permeability change by temperature amounts to higher than 0.025%/xc2x0 C. or lower than xe2x88x920.025%/xc2x0 C. in a temperature range of from 20xc2x0 C. to 80xc2x0 C. Therefore, the inductance of an electronic part making use of a molded or formed product (hereinafter may be referred to as xe2x80x9cmolded productxe2x80x9d merely) from such a resin composition greatly varies according to changes in environmental temperature. When the inductance greatly varies, a frequency band to be separated changes, and so the electronic part has been unable to be used as an electronic part for separating a specific frequency, such as a duplexer or multiplexer.
It is an object of the present invention to provide a resin composition which comprises a synthetic resin and a powdered magnetic material, has an extremely low rate of permeability change by temperature and can be applied to an application field of filters which separate a specific frequency, such as duplexers and multiplexers.
Another object of the present invention is to provide a molded product from such a resin composition.
The present inventors have carried out an extensive investigation with a view toward overcoming the above-described problems involved in the prior art. As a result, it has been found that soft ferrite powder having a rate of permeability change by temperature ranging from xe2x88x920.040 to 0.010%/xc2x0 C. in a temperature range of from 20xc2x0 C. to 80xc2x0 C. is used as a powdered magnetic material in combination with a synthetic resin, whereby the rate of permeability change by temperature of a molded product from a resin composition comprising the synthetic resin and the powdered magnetic material can be lowered within a range of xc2x10.025%/xc2x0 C., preferably xc2x10020%/xc2x0 C. It has also been found that when the average particle diameter and blending proportion of the soft ferrite powder are selected within respective specific ranges, a resin composition well balanced between magnetic properties such as permeability, and the molding and processing ability can be provided. The present invention has been led to completion on the basis of these findings.
According to the present invention, there is thus provided a resin composition comprising a synthetic resin and a powdered magnetic material, wherein:
(1) the powdered magnetic material is soft ferrite powder having a rate of permeability change by temperature ranging from xe2x88x920.040 to 0.010%/xc2x0 C. in a temperature range of from 20xc2x0 C. to 80xc2x0 C. and an average particle diameter ranging from 2 to 1,000 xcexcm, and
(2) the powdered magnetic material is contained in a proportion of 50 to 1,400 parts by weight per 100 parts by weight of the synthetic resin.
According to the present invention, there is also provided a molded or formed product obtained by molding or forming the resin composition.
Soft Ferrite Powder:
No particular limitation is imposed on the composition and production process of the soft ferrite powder useful in the practice of the present invention so far as it is soft ferrite powder having a rate of permeability change by temperature ranging from xe2x88x920.040 to 0.010%/xc2x0 C. in a temperature range of from 20xc2x0 C. to 80xc2x0 C. and an average particle diameter ranging from 2 to 1,000 xcexcm.
The soft ferrite is generally a compound (MOxc2x7Fe2O3) composed of ferric oxide (Fe2O3) and an oxide (MO) of a divalent metal. Examples of M include Ni, Mn, Co, Cu, Zn, Mg and Cd. Among various kinds of soft ferrite, soft ferrite having a composition represented by the general formula, (XO)x(ZnO)yFe2O3 is preferred. In the general formula, X means one or more of divalent metals such as Ni, Cu, Mg, Co and Mn. x and y denote a compositional ratio (molar ratio) of XO to ZnO. A molar ratio of (XO)x(ZnO)y(=x+y) to Fe2O3 is generally about 0.3:0.7 to 0.7:0.3, preferably about 0.4:0.6 to 0.6:0.4. Examples of such soft ferrite include Nixe2x80x94Zn ferrite, Mgxe2x80x94Zn ferrite and Mnxe2x80x94Zn ferrite.
In order to improve the permeability and the like of the soft ferrite used in the present invention, a small amount of additives, for example, SiO2, PbO, PbO2, As2O3, V2O5 and the like, may be added to the soft ferrite in the course of the preparation thereof. In the soft ferrite, it is also preferred to control the content of an iron oxide in order to suppress the deposition of hematite.
The soft ferrite powder used in the present invention can be obtained in accordance with the publicly known process such as the dry process, co-precipitation process or atomization and thermal decomposition process. Main raw materials of the soft ferrite are, for example, metal oxides such as Fe2O3, NiO, MnO2, ZnO, MgO, CuO, etc. and/or metal carbonates. In the dry process, the raw materials such as the metal oxides and/or the metal carbonates are mixed with each other with their blending proportions calculated so as to give a prescribed blending ratio, fired and then ground. In this dry process, it is preferred that the raw mixture be calcined at a temperature of 850 to 1,100xc2x0 C. and ground into fine particles and then granulated into granules, and the granules be further really fired and ground again to give soft ferrite powder having a desired average particle diameter. However, the raw mixture may be directly fired without calcining it. In the co-precipitation process, a strong alkali is added to an aqueous solution of metal salts to precipitate hydroxides, and the hydroxides are oxidized to give soft ferrite powder. In the atomization and thermal decomposition process, an aqueous solution of metal salts is subjected to thermal decomposition to give finely particulate oxides. In either the co-precipitation process or the atomization and thermal decomposition process, it is desired that a step of really firing be added after the granulation. Incidentally, the raw mixture may be really fired after calcination or directly.
Examples of a method for controlling the rate of permeability change by temperature of the soft ferrite powder low include {circle around (1)} a method in which a proportion of ZnO is made low, {circle around (2)} a method in which the kinds and amounts of additives to be used are adjusted, {circle around (3)} a method in which a firing temperature is adjusted, and {circle around (4)} combinations of these methods. The content of ZnO (or Zn component in ferrite) is made low, whereby the rate of permeability change by temperature of the resulting soft ferrite can be lowered. However, the permeability of the soft ferrite becomes lowered. On the other hand, when additives such as SiO2, PbO and PbO2 are added, the permeability of the resulting soft ferrite can be raised. Accordingly, when the content of ZnO, and the kinds and contents of the additives are adjusted, the rate of permeability change by temperature can be lowered while retaining a high permeability. For example, in the case where x+y in the above-described general formula is equal to 1, the rate of permeability change by temperature in a temperature range of from 20xc2x0 C. to 80xc2x0 C. can be lowered by controlling the proportion of y low to an extent of yxe2x89xa6about 0.4, preferably yxe2x89xa6about 0.3. The content of ZnO (or Zn component in ferrite) may be controlled to 20 mol % or lower, preferably 15 mol % or lower based on the whole composition of the soft ferrite. In this case, the lower limit of the content of ZnO is about 2 mol %. On the other hand, the proportions of the additives such as SiO2, PbO, PbO2, As2O3 and V2O5 are controlled within a range of about 5 to 15 wt. % in total, whereby the lowering of permeability can be prevented. In the case of Nixe2x80x94Zn ferrite, CuO is added in a small amount of about 0.5 to 3 wt. %, whereby the permeability can be raised like the above-described additives. However, it is preferred that the permeability be not very overraised in the case where the ferrite is used at high frequency.
The firing temperature varies according to the kind and composition of soft ferrite used. However, it is generally about 1,000 to 1,350xc2x0 C. The selection of this firing temperature permits lowering the rate of permeability change by temperature while retaining a moderate permeability. In order to improve magnetic properties of the resulting soft ferrite, it is preferred that such additives as described above be added, and the firing temperature be controlled at 1,050xc2x0 C. or higher.
In the present invention, after the firing step, the fired product (sintered material) may be ground into powder by any known method for the purpose of providing the intended soft ferrite powder. For example, a method, in which the sintered material is ground by a hammer mill, rod mill, ball mill or the like into powder having the intended particle diameter, may be used.
The average particle diameter of the soft ferrite used in the present invention is within a range of 2 to 1,000 xcexcm. If the average particle diameter of the soft ferrite powder is too great or small, the molding and processing ability of the resulting resin composition, such as injection molding or extrusion, is deteriorated. In particular, if the average particle diameter of the soft ferrite powder is too great, the abrasion of a molding or forming machine is allowed to extremely proceed, and so the molding or forming of the resulting resin composition becomes difficult. If the average particle diameter of the soft ferrite powder is too small, it is difficult to achieve a sufficient permeability in the resin composition. The average particle diameter of the soft ferrite powder is preferably about 2 to 500 xcexcm, more preferably about 3 to 350 xcexcm.
The rate of permeability change by temperature in a temperature range of from 20xc2x0 C. to 80xc2x0 C. of the soft ferrite powder according to the present invention is within a range of xe2x88x920.040 to 0.010%/xc2x0 C. The use of the soft ferrite powder having such a low rate of permeability change by temperature permits the provision of molded products low in rate of permeability change by temperature in a temperature range of from 20xc2x0 C. to 80xc2x0 C. and suitable for use in filters such as duplexers and multiplexers. The rate of permeability change by temperature in a temperature range of from 20xc2x0 C. to 80xc2x0 C. of the soft ferrite powder according to the present invention is preferably within a range of xe2x88x920.035 to 0.008%/xc2x0 C., more preferably xe2x88x920.030 to 0.005%/xc2x0 C. In many cases, the upper limit thereof is 0.000%/xc2x0 C.
Resin Composition:
Examples of the synthetic resin useful in the practice of the present invention include polyolefins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymers and ionomers; polyamides such as nylon 6, nylon 66, nylon 6/66, nylon 46 and nylon 12; poly(arylene sulfides) such as poly(phenylene sulfide), poly(phenylene sulfide ketone) and poly(phenylene sulfide sulfone); polyesters such as polyethylene terephthalate, polybutylene terephthalate and overall aromatic polyesters; polyimide resins such as polyimide, polyether imide and polyamide-imide; styrene resins such as polystyrene and acrylonitrile-styrene copolymers; chlorine-containing vinyl resins such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymers and chlorinated polyethylene; poly(meth)acrylates such as polymethyl acrylate and polymethyl methacrylate; acrylonitrile resins such as polyacrylonitrile and polymethacrylo-nitrile; thermoplastic fluorocarbon resins such as tetrafluoroethylene/perfluoroalkyl vinyl ether copolymers, polytetrafluoroethylene, tetrafluoro-ethylene/hexafluoropropylene copolymers and polyvinylidene fluoride; silicone resins such as dimethyl polysiloxane; various kinds of engineering plastics such as polyphenylene oxide, poly(ether ether ketone), poly(ether ketone), polyallylate, polysulfone and poly(ether sulfone); various kinds of thermoplastic resins such as polyacetal, polycarbonate, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polybutylene, polyisobutylene, polymethylpentene, butadiene resins, polyethylene oxide, oxybenzoyl polyester and poly-p-xylene; thermosetting resins such as epoxy resins, phenol resins and unsaturated polyester resins; elastomers such as ethylene-propylene rubber, polybutadiene rubber, styrene-butadiene rubber and chloroprene rubber; thermoplastic elastomers such as styrene-butadiene-styrene block copolymers; etc.
These synthetic resins may be used either singly or in any combination thereof. Of these synthetic resins, polyolefins such as polyethylene and polypropylene, polyamides, and poly(arylene sulfides) such as poly(phenylene sulfide) are particularly preferred from the viewpoint of moldability. From the viewpoints of moldability, heat resistance, etc., poly(arylene sulfides) and polyamides are particularly preferred.
The resin compositions according to the present invention comprise the powdered magnetic material (soft ferrite powder) in a proportion of 50 to 1,400 parts by weight per 100 parts by weight of the synthetic resin. If the blending proportion of the powdered magnetic material is too low, it is difficult to provide a resin composition and a molded product which have a permeability fit for the purpose of use. If the blending proportion of the powdered magnetic material is too high, the flowability of the resulting resin composition is deteriorated, resulting in the difficulty of conducting melt processing such as injection molding or extrusion. The blending proportion of the powdered magnetic material is preferably 70 to 1,300 parts by weight, more preferably 80 to 1,200 parts by weight.
In a resin composition comprising a synthetic resin and a powdered magnetic material, soft ferrite powder having a rate of permeability change by temperature ranging from xe2x88x920.040 to 0.010%/xc2x0 C. in a temperature range of from 20xc2x0 C. to 80xc2x0 C. is used as the powdered magnetic material, whereby the rate of permeability change by temperature in a temperature range of from 20xc2x0 C. to 80xc2x0 C. of a molded product obtained from such a resin composition can be controlled within a range of xc2x10.025%/xc2x0 C. If the rate of permeability change of the soft ferrite used exceeds 0.010%/xc2x0 C., the rate of permeability change by temperature of the molded product generally comes to exceed 0.025%/xc2x0 C. If the rate of permeability change of the soft ferrite used is lower than xe2x88x920.040%/xc2x0 C. on the other hand, the rate of permeability change by temperature of the molded product generally becomes lower than xe2x88x920.025%/xc2x0 C. When such a resin composition having a high rate of permeability change by temperature is used to produce a filter such as a duplexer or multiplexer, the inductance thereof greatly varies according to changes in environmental temperature, and so a frequency band to be separated changes. Therefore, such a filter comes to be lacking in practicability.
The permeability of a molded product from the resin composition according to the present invention varies according to the permeability and blending proportion of the soft ferrite powder. However, it is generally at least 1.5, preferably at least 1.7. In many cases, the permeability may be controlled to at least 2.0. If the permeability of the molded product is too low, the molded product becomes unsuitable for use in a filter.
Various kinds of fillers such as fibrous fillers, plate-like fillers and spherical fillers may be incorporated into the resin compositions according to the present invention with a view toward improving their mechanical properties, heat resistance and the like. Among these fillers, the fibrous filler such as glass fiber is preferred from the viewpoint of enhancing mechanical strength. No particular limitation is imposed on the blending proportion of the filler. However, it is generally 100 parts by weight or lower, preferably 50 parts by weight or lower, per 100 parts by weight of the synthetic resin. The blending of the filler is optional, and the lower limit of the blending proportion thereof is 0 part by weight. If blended, however, it is desirable that the blending proportion be controlled to generally at least 5 parts by weight, preferably at least 10 parts by weight, per 100 parts by weight of the synthetic resin.
Various kinds of additives such as flame retardants, antioxidants and colorants may also be incorporated into the resin compositions according to the present invention as needed.
The resin compositions according to the present invention can be produced by uniformly mixing the respective components. For example, the respective prescribed amounts of the powdered magnetic material, the synthetic resin, and the various kinds of additives if desired are mixed by a mixer such as a Henschel mixer, and the mixture is melted and kneaded, whereby a resin composition can be produced.
The resin compositions according to the present invention can be formed into molded or formed products of desired shapes by various kinds of molding or forming processes such as injection molding, extrusion and compression molding. Since the resin compositions according to the present invention can be molded or formed by such various kinds of melt processing techniques, molded products of complex shapes, small-sized molded products and the like may be formed with ease. No particular limitation is imposed on the kind of a molded product from the resin composition. However, the resin composition is preferably formed into a molded product (for example, a magnetic core) suitable for use in a filter such as a duplexer or multiplexer, since its rate of permeability change by temperature is extremely low.
The present invention will hereinafter be described more specifically by the following Examples and Comparative Examples. However, the present invention is not limited to these examples only.
Physical properties in the examples were measured in accordance with the following respective methods:
(1) Rate of permeability change by temperature of powdered magnetic material:
Each powdered magnetic material sample was packed in a hermetically sealed glass tube having a diameter of about 6 mm, and the glass tube was wound with 50 turns of a polyurethane-coated conductor having a diameter of 0.3 mm to form a coil. With respect to this coil, the inductance at a frequency of 100 kHz was measured at respective temperatures of 20xc2x0 C. and 80xc2x0 C. by means of an LCR meter (4192A manufactured by Hewlett Packard Co.). The rate of permeability change by temperature of the sample was calculated out in accordance with the following equations {circle around (1)} to {circle around (3)}:
{circle around (1)} L80=inductance at 80xc2x0 C.;
{circle around (2)} L20=inductance at 20xc2x0 C.; and
{circle around (3)} Rate of permeability change by temperature (%/xc2x0 C.)=[(L80xe2x88x92L20)/L20]/60xc3x97100
(2) Permeability of molded product and its rate of permeability change by temperature:
The permeability of each molded product sample was measured in accordance with JIS C 2561. The rate of permeability change by temperature of the molded product sample was determined in the following manner. Namely, a troidal core having an outer diameter of about 13 mm, an inner diameter of 7.5 mm and a thickness of 5 mm was made by molding to use a sample. This sample was wound with 60 turns of a polyurethane-coated conductor having a diameter of 0.3 mm to form a coil. With respect to this coil, the inductance at a frequency of 100 kHz was measured at respective temperatures of 20xc2x0 C. and 80xc2x0 C. by means of the LCR meter (4192A manufactured by Hewlett Packard Co.) in accordance with JIS C 2561. The rate of permeability change by temperature of the molded troidal core sample was calculated out using the above-described equations {circle around (1)} to {circle around (3)}.
(3) Average particle diameter of powdered magnetic material:
Each powdered magnetic material sample was taken out twice by a microspatula and placed in a beaker. After 1 or 2 drops of an anionic surfactant (SN Dispersat 5468) were added thereto, the sample was kneaded by a rod having a round tip so as not to crush the powdered sample. The thus-prepared sample was used to determine an average particle diameter by means of a Microtrack FRA particle diameter analyzer 9220 model manufactured by Nikkiso Co., Ltd.